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Assistant Professor, Department of Civil Engineering, Arkansas State University, PO Box 1740,
LSW#239, State University, Arkansas 72467, USA, E-mail: mhossain@astate.edu
2
David Ross Boyd Professor and Aaron Alexander Professor, Associate Dean for Research and
Graduate Programs, College of Engineering, University of Oklahoma, 202 W. Boyd ST #107, Norman,
OK 73019, USA
3
Associate Professor, School of Aerospace and Mechanical Engineering, The University of Oklahoma,
865 Asp Avenue, Felgar Hall, 212, Norman, OK 73019, USA
4
Assistant Professor, School of Aerospace and Mechanical Engineering, The University of Oklahoma,
865 Asp Avenue, Felgar Hall, 212, Norman, OK 73019, USA
.
ABSTRACT: Due to an increasing rate of traffic volume and truck loads in recent
years, neat asphalt binders are often modified with expensive polymers for increased
stiffness. Nanoclays, on the other hand, are relatively inexpensive and naturally
abundant, and have favorable intrinsic properties (e.g., nanoscopic size and surface
area). Although the stiffness of nanoclay-modified binder is reported to increase, its
moisture resistance remains unknown. To this end, the current study investigated
moisture resistance of a performance grade binder (PG 64-22OK) modified with
different dosages of a selected nanoclay (Cloisite 15A) through the surface free
energy (SFE) technique. The state of dispersion of the nanoclay in the binder was
examined using scanning electron microscope and small angle X-ray diffraction
(SAXD) techniques. The cohesive energy of nanoclay-modified binder was found to
be lower than that of the base binder. The adhesive energy between eight different
aggregates (sandstone, gravel, granite, basalt, and limestone from four sources) and
2% nanoclay-modified binder in dry condition decreased up to 22%. The adhesion
energy in wet condition reduced up to 24%. The compatibility ratio (CR) values of
different aggregates with the nanoclay-modified binders show significant decrease in
bond strength in cases of all aforementioned aggregates except granite.
INTRODUCTION
Over 90% of paved roads in the U.S. are asphalt pavements, and the annual
expenditures for the maintenance of these pavement infrastructures exceed $100
billion (NECEPT 2012). Although a small amount (about 5%), asphalt binder plays a
major role on the performance of the hot mix asphalt (HMA) pavements. Now-a-days,
polymer additives (e.g., styrene-butadiene-styrene (SBS)) are used to enhance
mechanistic properties such as increased rut and crack resistance of asphalt binders.
The addition of polymers increases the overall cost of asphalt binders and mixes. On
the other hand, nanoclays posses an extraordinary potential for improving the
performance of asphalt binder and asphalt mixes due to their nanoscale phenomena
such as the quantum effects, structural features, high surface energy, spatial
confinement and large fraction of surface atoms. Moreover, nanoclays are fairly
inexpensive, naturally abundant and sustainable materials for the construction of
asphalt pavements. Thus, a significant portion of the current usage of polymermodified binders can potentially be replaced by nanoclay-modified binders for
improved mechanical and functional characteristics of the asphalt pavements.
Nanoclays are layered silicates that are found naturally and hence they are
environmentally safe, economical, and sustainable. One of the most frequently used
layered silicates is montmorillonite (MMT), which has a 2:1 layered structure with
two silica tetrahedron layers sandwiching an alumina octahedron layer. These three
layers together form one clay sheet that has a thickness of about one nm (one-billionth
of a meter), thus the individual clay sheets are classified as nanomaterial, although
the lateral dimensions of the individual clay sheet can vary from 100 nm to a few
microns with unusually high aspect ratio (NNI, 2013). On the other hand, a portion of
fine-grained soil that consists of one or more clay minerals (e.g., hydrous aluminium
phyllosilicates) with traces of metal oxides and organic matter which is finer than
0.002 millimeter.
A number of physical, mechanical and rheological properties of polymer binders are
successfully enhanced by the addition of a small amount of nanomaterials, 1-5
percent by weight (Saha et al. 2010). Due to their enormous surface area and energy,
nanoclays have huge potential as modifier to improve asphalt binders performance
properties (e.g., rutting). Untreated nanoclay sheets are held together due to high
metallic cations presence on the surface, giving a low inter-gallery spacing (about
11.7oA). Organic treatments are often used to increase the inter-gallery spacing so that
polymer molecule can penetrate between the inter-gallery spacing of the silicate
layers. When the polymer molecules penetrate between the adjacent layers of the
nanoclay sheets, the gallery spacing is increased and the resulting morphology is
called intercalated structure. An exfoliated morphology occurs when the clay platelets
are extensively delaminated and completely separated as a result of through polymer
penetration. Schematic of different morphology of nanoclay-polymer structure is
shown in Fig. 1. Although various dispersion techniques, in combination with
coupling agents, are used, creating an exfoliated nanoclay structure in a stable manner
is a challenging task.
Even though the advancement of nanotechnology research has increased in recent
years, limited studies attempted to investigate the application in asphalt pavements.
You et al. (2011) studied effects of two unspecified nanoclays on a PG 58-34 binder.
It is reported that with the 2% nanoclay-modified binder the complex shear modus
(G*) increased about 66% while the 4% nanoclay-modified binder the G* values
increased by 125%. This study also reported significant increase in viscosity of the
nanoclay modified binders. In a study by Jahromi and Ahmadi (2011), it is reported
that both the Cloisite15A and Nanofil15 modifications on a viscosity grade AC-10
binder increased the stiffness and rutting resistance, indirect tensile strength, and
resilient modulus, but reported decreased fatigue performance. These researchers
reported that nanoclay was found to increase the viscosity of the neat binder.
However, none of the studies focused on the preparation and mechanistic evaluation
nanoclay-modified asphalt binders for conditions (e.g., binder source and grade,
climate conditions, and design specifications) prevailing in Oklahoma.
The main objectives of the proposed study are to prepare nanoclay-modified asphalt
binders and to investigate the effects on nanoclays on moisture resistance of the neat
asphalt binder. To achieve these objectives, the current study evaluates the effects of
dosage levels of a selected nanoclay on surface free energies and compatibility ratios
of nanoclay-modified binders.
MATERIALS AND METHODOLOGY
Materials
The current project evaluated a commonly used unmodified PG 64-22OK binder
modified with different dosages (1%, 2% and 4% by the weight of the binder) of
nanoclay (Cloisite 15A). The PG 64-22OK was obtained from Valero refinery at
Ardmore, Oklahoma. Cloisite 15A nanoclay powder was obtained from Southern
Clay Products. The Cloisite 15A is a natural montmorillonite modified with a
quaternary ammonium salt. The average particle size is about 13 micron with average
d-spacing of 31.5 Angstrom. The average density is about 1.66 g/cc.
Mixing Nanoclay and Asphalt Binder
Roughly 175 gm of the neat binder was heated in a glass container to 150oC for
about 2 hours to achieve the processing viscosity. Then the nanoclay was added to the
heated asphalt binder while slowly stirring the mixture using the magnetic stir bar.
The speed was slowly increased and fixed to about 500 rpm while maintaining the
mixing temperature of 150oC using a thermocouple connected to the hot plate. The
mixing was continued for about 2 hours to achieve uniform dispersion of the nanoclay
in the asphalt binder.
Dispersion Characterization
The dispersion of nanoclay in asphalt binders was examined at nanoscale level
using both scanning on electron microscope (SEM) and small angle X-ray diffraction
(SAXD) techniques. Both SEM and SAXD data are compared to achieve a conclusion
on the level of dispersion and efficiency of the blending process. In the SAXD
technique, Braggs law of diffraction is used to measure d-spacing between the
nanoclay sheets. Spacing change (increase or decrease) information can be used to
determine the type of dispersion. For example, no d-spacing change indicates
immiscible, increase in d-spacing indicates intercalated, and no distinct peak in the
signal indicates exfoliation.
Effect of moisture on the theoretical bond strength (adhesive and cohesive) was
evaluated based on SEF components using using the Good Van Oss-Chaudhury
theory (van Oss et al., 1988). A dynamic contact angle analyzer (Fig. 2) was used in
this study for measuring the contact angles of asphalt binder with three reference
solvents (water, glycerin and formamide). This analyzer follows the Wilhelmy plate
method, which determines the contact angle at the solid-liquid interface by measuring
the force exerted by the meniscus on the sample.
FIG. 2.
(a)
(b)
(a) DCA assembly, (b) DCA samples coated with asphalt binder.
(a)
(b)
(c)
(d)
FIG. 3. Nanoclay dispersion analysis: (a) optical microscope, (b) SEM analysis,
(c) SAXD data with 2% nanoclay, and (d) SAXD data with 4% nanoclay.
From the SAXD data (Figs. 3c and 3d), it is seen that the Closite 15A samples with
2% and 4% show peak at 2-theta values of 1.934o and 1.991o, respectively. The
corresponding d-spacing values are 45.7 angstrom and 44.3 angstrom. Comparing the
d-spacing value of Cloisite 15A of 31.5 angstrom, the increased value of d-spacing
indicates that the 2% and 4% nanoclay modified samples show intercalated
microstructure. This is an indication of fairly exfoliated microstructure, which implies
further investigation is needed to achieve a fully exfoliated system.
Moisture Resistance
As noted earlier, the wetting ability of any surface by a solvent can be determined
by the contact angle made by the solvent with the surface. A general trend is if the
contact angle is close to zero, then the solvent is spreading on the surface completely;
if it is less than 90o, then it is wetting the surface of the material; if it is greater than
90, it is not wetting the surface completely. Results for the contact angle
measurements with three solvents are shown in Fig. 4a. An increasing trend was
observed in the contact angle of the nanoclay-modified PG 64-22 with water,
formamide, and glycerin. Two-tailed unequal variance Students t-test results at 95%
confidence interval showed significant differences in the contact angles with the
addition of nanoclay at 1% and above in the PG 64-22 binder compared to
unmodified binder. This implies less wetting of the substrate when nanoclay is mixed
with the binder. Further, no clear trend in contact angles between unaged and RTFOaged conditions of the 2% nanoclay-modified binder.
The variations in the SFE characteristics of PG 64-22 binder modified with selected
percentages of nanoclay are presented in Fig. 4b. The total SFE of PG 64-22
increased with a small amount (1%) of nanoclay, which is mostly due to the
significant increase of the nonpolar Lifshitz-van der Waals component (aLW). The
acidic nature of the asphalt binder (a+) increased with the amount of nanoclay. There
is no particular trend (increase or decrease) in the basic SFE component of the binder
when nanoclay is used. Even though the acidic nature of the binder decreases with the
addition of nanoclay, the net increase of the total SFE is due to the increase of the
aLW component.
As mentioned earlier, the CR value indicates the compatibility of an asphalt binder
and aggregate system. The work of adhesion values under dry and wet conditions of
nanoclay-modified binders and different aggregates were used to calculate their CR
values. The SFE components of these acidic (sandstone, gravel, granite and basalt)
and basic (limestones) aggregates are obtained from the literature (Bhasin et al. 2007).
From the CR values, as shown in Fig. 4c, it is observed that nanoclay is expected to
reduce the moisture resistance of all of the asphalt and aggregate systems except for
the asphalt and granite system. Among the studied acidic aggregates, with and
without nanoclays, basalt is the most compatible, which is followed by granite, which
is followed by either sandstone or gravel. However, the reduction in CR values due to
the addition of nanoclay is the highest in the case of either basalt or gravel, which is
followed by sandstone, which is followed by granite. There is virtually no difference
in the normalized CR reductions between gravel and basalt systems. The normalized
CR reductions of limestone and asphalt systems lie somewhere between those of
gravel and asphalt, and sandstone and asphalt systems. Furthermore, the CR of the
binder and aggregate system reduces when additional nanoclay is added in the binder.
(a)
(b)
(c)
FIG. 4. Variation of: (a) contact angle, (b) SFE components, and (c) CR values.
CONCLUSIONS
The SFE data of the current study suggests that the compatibility of aggregate and
binder systems reduces when nanoclay is blended with the neat binder. Among the
different aggregates, basalt is the most compatible and gravel is the least compatible
aggregate with nanoclay-modified binders. However, the reduction of compatibility
is the lowest in the case of granite when nanoclay is added in the neat binder.
Findings of the current study also suggest that the binder has to be blended with the
nanoclay so that it is fully exfoliated. Findings of the current study also imply